Dyeing of human keratin materials by dry thermal transfer of a direct dye, composition comprising the said dye and its method of preparation

ABSTRACT

The subject of the present invention is the use, for dyeing in particular human keratin materials, of a direct dye, in particular an azo dye, by dry thermal transfer. Its subject is furthermore a method for dyeing keratin materials, n which at least one direct dye, in particular one azo dye, contained in a dry composition, is applied to or close to the keratin materials, and a source of heat is applied, causing the thermal transfer of the direct dye(s) at the surface and/or inside the keratin materials. It relates furthermore to the dry composition and a method for preparing it.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a National Phase application based on PCT/EP2006/002586 filed on Feb. 11, 2006, the contents of which are incorporated herein by reference and claims the priority of French Application No. 0502031, filed on Feb. 28, 2005, and the benefit of U.S. Provisional Application No. 60/681,957, filed on May 18, 2005, the contents of both of which are incorporated herein by reference.

The subject of the present invention is the use, for dyeing in particular human keratin materials, of a direct dye by dry thermal transfer. Its subject is furthermore a method for dyeing keratin materials in which a dry solid composition comprising the said direct dye is used. It relates furthermore to the composition and its method of preparation.

The invention relates more particularly to the field of dyeing human keratin fibres, and in particular hair.

It has been known for a long time to modify the colour of hair, and in particular to mask grey hair.

Essentially two types of technology are known which are used to dye human keratin fibres.

The first method, called direct or semipermanent dyeing, consists in changing or providing colour by the application of a coloured molecule which penetrates by diffusion into the fibre and/or remains adsorbed at its surface.

The second method, called oxidation dyeing or permanent dyeing, consists in changing or providing colour using, on the very inside of the fibre, an oxidative condensation of dye precursors which are weakly coloured or colourless compounds. After this reaction, the dyes formed are insoluble and are trapped inside the fibre.

The two methods summarized above make it possible to obtain numerous colours.

On the other hand, these methods are used with liquid compositions, which has the consequence of making these methods “messy” for clothes, hairdressing accessories (combs, towels and the like), tubs and the like.

Moreover, the dyeing times are generally long because the time for rinsing the product and the time for drying the hair should be added to the leave-in time for the composition.

Finally, the use of some dyes offering good dyeing performance on the fibres is sometimes limited because of their low solubility in liquid formulation carriers.

As can be seen, there is a constant search for methods for dyeing human keratin materials which, while allowing effective dyeing to be obtained, do not have the disadvantages mentioned above.

The subject of the present invention is therefore a method for dyeing keratin materials which make it possible to rapidly dye hair using thermal transfer of dyes, and in particular of specific azo dyes.

This method has the advantage of not requiring the use of a liquid formulation carrier for the dye, which makes the dyeing particularly scarcely messy.

Furthermore, the fact that a liquid carrier is not required and that the dyes are used in a solid form makes it possible to use dyes which are sparingly soluble or which are unstable in conventional dyeing media. This can contribute to further broadening the pallet of colours possible.

Moreover, still by virtue of the fact that the dye is initially used in a solid form, there is no need either for rinsing, or for shampooing and/or for drying the materials treated.

Furthermore, thermal transfer being rapid, the leave-in times are short.

The latter two factors contribute to making the method according to the invention more rapid than conventional methods.

Finally, this method makes it possible to produce, in a simple manner, motifs on the materials treated, in particular on the hair.

Thus, the first subject of the present invention is the use of at least one direct dye for dyeing in particular human keratin materials by dry thermal transfer.

Its subject is likewise a method for dyeing in particular human keratin materials, in which at least one direct dye contained in a dry composition is applied to or close to the keratin materials, and a source of heat is applied, causing the thermal transfer of the direct dye(s) at the surface and/or inside the keratin materials.

Its subject is furthermore a dry composition, in the form of a divided or undivided solid, comprising at least one direct dye and at least one film-forming polymer.

Finally, its subject is a method for preparing this composition, in which a mixture comprising at least one direct azo dye, at least one film-forming polymer and at least one solvent are applied to a support, and then the said solvent is evaporated.

However, other characteristics and advantages of the present invention will emerge more clearly on reading the description and the examples which follow.

In the text which follows, when it is specified that the composition is “dry”, that means that the variation in the dry extract of such a composition, measured before and after a thermal treatment in an oven for one hour at 100° C., varies by 20% by weight or less, preferably by 10% by weight or less.

It is recalled that a solid compound is a compound which does not flow or does not undergo deformation when it is subjected to moderate forces. It should be noted that when the compound is in the form of a divided solid, the characteristics which have just been recalled apply at the level of the particle and not of a combination of particles deposited or otherwise on a support.

Moreover, the expression thermal transfer is understood to mean, for the purposes of the present invention, the application of heat to the dry composition brought into contact with the keratin materials to be treated or close to them. This heat is obtained by means of a source at a temperature more particularly between 100 and 500° C., advantageously between 130 and 250° C. and preferably between 140 and 220° C.

Preferably, this source of heat is brought into contact with the whole of the dry composition and keratin materials to be treated.

Without being bound by any theory, one of the possible mechanisms for dyeing keratin materials involves a step of vaporization or sublimation of the direct dye present in the dry composition according to the invention.

Human keratin materials denote more generally keratin fibres, such as hair or the eyelashes.

It should finally be recalled that, unless otherwise stated, the limits delimiting a range of values form part of this range.

As indicated above, this method according to the invention is carried out using at least one direct dye.

Suitable are the direct dyes customarily used in the field for dyeing keratin fibres. These dyes may be non-ionic, cationic or anionic.

By way of examples of suitable dyes, there may be mentioned the acridine, acridone, anthranthrone, anthrapyrimidine, anthraquinone, azine, azo, azomethine, benzanthrone, benzimidazole, benzimidazolone, benzindole, benzoxazole, benzopyran, benzothiazole, benzoquinone, bisazine, bisisodinoline, carboxanilide, coumarin, cyanine (such as for example azacarbocyanine, diazacarbocyanine, diazahemicyanine, hemicyanine, tetraazacarbocyanine), diazine, diketopyrrolopyrrole, dioxazine, diphenylamine, diphenylmethane, dithiazine, flavonoid such as flavanthrone and flavone, fluoroindine, formazan, hydrazone in particular arylhydrazone, hydroxyketone, indamine, indanthrone, indigoid, and pseudo-indigoid, indophenol, indoaniline, isoindoline, isoindolinone, isoviolanthrone, lactone, methine, naphthalimide, naphthanilide, naphtholactam, naphthoquinone, nitro(hetero)aromatic, oxadiazole, oxazine, perilone, perinone, perylene, phenazine, phenothiazine, phthalocyanine, polyene/carotenoid, porphyrine, pyranthrone, pyrazoloanthrone, pyrazolone, pyrimidinoanthrone, pyronine, quinacridone, quinoline, quinophthalone, squarane, stilbene, tetrazolium, thiazine, thioindigo, thiopyronine, triarylmethane and xanthene dyes, alone or as mixtures.

According to a particularly advantageous embodiment of the invention, the direct dye is chosen from azo dyes.

Preferably, the azo dye corresponds to the following formula (I):

in which:

-   n and n′, which are identical or different, represent an integer     between 1 and 5 inclusive, -   R, which are identical or not, R′, which are identical or not,     independently of each other, represent     -   a hydrogen atom;     -   a linear, branched or cyclic, saturated, unsaturated or         aromatic, C₁-C₃₀ hydrocarbon chain,         -   optionally substituted with one or more halogen atoms; with             one or more groups, which are identical or not, chosen from             the groups hydroxyl; nitro; cyano; carboxylic acid; allyl;             haloallyl; C₁-C₁₀ alkoxy; (C₁-C₄)alkylcarbonyl-amino;             (C₁-C₄)alkylaminocarbonyl; hydrogenocarbonylamino;             (C₁-C₄)alkylsulphonylamino; (C₁-C₄)alkoxycarbonylamino;             (C₁-C₄)alkoxycarbonyl;             (C₁-C₄)alkylcarbonyl(C₁-C₄)alkoxycarbonyl; CF₃; amino; amino             optionally substituted with one or more radicals which are             identical or different, C₁-C₁₀ alkyl, C₁-C₁₀ hydroxyalkyl,             alkoxy-(C₁-C₁₀)alkyl, C₁-C₁₀ aminoalkyl,             (C₁-C₁₀)(di)alkyl-amino(C₁-C₁₀)alkyl, C₁-C₁₀ cyanoalkyl,             C₆-C₃₀ aryl, (C₆-C₃₀)aryl(C₁-C₄)alkyl,             (C₄-C₃₀)cyclo-(C₁-C₁₂)alkyl, (C₁-C₄)alkylcarbonyl,             (C₁-C₄)alkyl-carboxy (C₁-C₄)alkyl, allyl, haloallyl;         -   optionally interrupted or attached to the aromatic ring via             one or more heteroatoms and/or groups comprising one or more             heteroatoms chosen from oxygen, sulphur, nitrogen;     -   a group hydroxyl; C₁-C₄ alkoxy; carboxylic acid; amino; amino         substituted with one or more radicals, which are identical or         different, chosen from the radicals C₁-C₄ alkyl, C₂-C₄ alkenyl,         C₁-C₄ cyanoalkyl, C₁-C₄ hydroxyalkyl, C₆-C₃₀ aryl,         (C₆-C₃₀)aryl(C₁-C₄)alkyl, allyl, (C₁-C₄)alkoxy(C₁-C₄)alkyl,         (C₄-C₃₀)cyclo(C₁-C₁₂)-alkyl, (C₁-C₄)alkylcarbonyl,         (C₁-C₄)alkylcarboxy (C₁-C₄)alkyl, haloallyl, (C₁-C₄)aminoalkyl,         (C₁-C₄)(di)alkylamino(C₁-C₄)alkyl, (C₁-C₄)-alkylsulphonyl,         (C₁-C₄)alkoxycarbonyl; halogen; allyl; hydrogenocarbonyl;         trifluoromethyl; nitro; cyano;         it being understood that at least one of the radicals R or R′         represents a group hydroxyl; nitro; cyano; amino; amino         optionally substituted with one or more radicals; and         optionally two radicals R carried by two adjacent carbon atoms         or two radicals R′ carried by two adjacent carbon atoms may form         with the aromatic ring carrying the carbon atoms to which each         is attached a fused ring of the naphthalene type optionally         substituted with an aminosulphonyl or (C₁-C₄)alkylaminosulphonyl         group.

Preferably, the direct azo dye corresponds to the following formula (Ia):

in which:

-   -   R′₁ represents a hydrogen atom, an amino group or a hydroxyl         group;     -   R′₂ represents a hydrogen atom, a halogen atom, a carboxylic         acid group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, an allyl         group or a C₁-C₄ aminocarbonylalkyl group;     -   R′₃ represents a hydrogen atom, a hydroxyl group or a group of         the NR′₁R′₂ type where R′₁ and R′₂ represent, independently of         each other, a hydrogen atom, a C₁-C₄ alkyl group, a C₂-C₄         alkenyl group, a C₁-C₄ cyanoalkyl group, a C₁-C₄ hydroxyalkyl         group, a C₆-C₃₀ aryl group, a (C₆-C₃₀)aryl(C₁-C₄)alkyl group, an         allyl group, a (C₁-C₄)alkoxy(C₁-C₄)alkyl group, a         (C₄-C₃₀)cyclo(C₁-C₁₂)alkyl group, a (C₁-C₄)alkyl-carbonyl group,         a (C₁-C₄)alkylcarboxy(C₁-C₄)alkyl group or a haloallyl group, a         C₁-C₄ aminoalkyl group, a (C₁-C₄)(di)alkylamino(C₁-C₄)alkyl         group;     -   R′₂ and R′₃ may form, with the benzene ring, a fused ring of the         naphthalene type optionally substituted with a group —SO₂—NHR         where R represents a hydrogen atom or an optionally substituted         C₁-C₄ alkyl chain;     -   R′₄ represents a hydrogen atom, a halogen atom, a hydroxyl         group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a         (C₁-C₄)alkoxy(C₁-C₄)alkyl group;     -   R′₅ represents a hydrogen atom, a halogen atom, a hydroxyl         group, an amino group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy         group, a (C₁-C₄)alkylcarbonylamino group, a         hydrogenocarbonylamino group, a (C₁-C₄)alkylsulphonylamino         group, a (C₁-C₄)alkoxycarbonylamino group or a CF₃ group;     -   R′₄ and R′₅ may form, with the benzene ring, a fused ring of the         naphthalene type;     -   R₁ represents a hydrogen atom, a halogen atom, a hydroxyl group,         a nitro group or a cyano group;     -   R₂ represents a hydrogen atom, a nitro group or a C₁-C₄ alkyl         group;     -   R₃ represents a hydrogen atom, a C₁-C₄ alkyl group, a C₁-C₄         alkoxy group, a (C₄-C₃₀)cyclo(C₁-C₁₂)alkyl group, a C₂-C₄         alkenyl group, a C₁-C₄ alkoxycarbonyl group, a         (C₁-C₄)alkylcarbonyl group, a         (C₁-C₄)alkoxycarbonyl(C₁-C₄)alkoxycarbonyl group, a         (C₁-C₄)alkylcarbonyl(C₁-C₄)alkoxycarbonyl group, an aryl group,         an amino group, a nitro group, a cyano group or a CF₃ group;     -   R₄ represents a hydrogen atom or a nitro group;     -   R₅ represents a hydrogen atom, a halogen atom, a carboxylic acid         group, a hydroxyl group, an amino group, a cyano group or a         C₁-C₄ alkyl group;         it being understood that at least one of the radicals R′₁ to R′₅         and R₁ to R₅ represents a group hydroxyl; nitro; cyano; amino;         amino optionally substituted with one or more radicals.

According to an advantageous embodiment, the radicals R′₁, R′₂, R₁, R₂, R₄ represent a hydrogen atom.

More particularly, the radical R′₃ represents a hydrogen atom, a group of the NR″₁R″₂ type where R″₁ and R″₂ represent, independently of each other, a hydrogen atom, a C₁-C₄ alkyl group, a C₁-C₄ cyanoalkyl group, a C₁-C₄ hydroxyalkyl group, a C₁-C₄ aminoalkyl group.

As regards the radical R′₄, it represents more particularly a hydrogen atom.

Preferably, the radical R′₅ represents a hydrogen atom, a C₁-C₄ alkyl group.

According to another embodiment, the radicals R′₄ and R′₅ form, with the benzene ring, a fused ring of the naphthalene type.

The radical R₃ represents more particularly an amino group, a nitro group.

The radical R₅ represents more particularly a hydrogen atom; a halogen atom, preferably chlorine, fluorine; an amino group.

Preferably, the direct dye used in the context of the present invention, and advantageously the direct azo dye, is chosen from compounds having an enthalpy of vaporization of less than or equal to 200 kJ/mol.

In accordance with an advantageous embodiment of the invention, the direct azo dye is chosen from the following direct dyes: Solvent Brown 1 [6416-57-5], Solvent Orange 1 [2051-85-6], Solvent Orange 7 [3118-97-6], Solvent Yellow 2 [60-11-7], Solvent Yellow 3 [97-56-3], Solvent Yellow 7 [1689-82-3], Solvent Yellow 14 [842-07-9], Disperse Orange 1 [2581-69-3], Disperse Orange 3 [730-40-5], Disperse Orange 25 [31482-56-1], Disperse Red 1 [2872-52-8], Disperse Red 13 [3180-81-2], Disperse Red 19 [2734-52-3], Disperse Red 50 [12223-35-7]+[40880-51-1], Disperse Yellow 3, Mordant Brown 4 [6247-28-5], Mordant Brown 6 [6247-28-5], Mordant Brown 24 [6370-46-3], Mordant Brown 48 [6232-53-7], Mordant Orange 1 [2243-76-7], Pigment Red 3 [2425-85-6], 4-dimethylamino-2-methylazobenzene [54-88-6], 2-(4-diethylaminophenylazo)benzoic acid [76058-33-8], N-ethyl-N-(2-aminoethyl)-4-(4-nitro-phenylazo)aniline, N,N-hydroxyethyl-4-(4-nitrophenyl-azo)-2-methylaniline, N,N-hydroxyethyl-4-(4-amino-phenylazo)-2-aniline, and mixtures thereof.

The method according to the invention therefore consists in applying at least one direct dye, contained in a dry composition, to or close to keratin materials, and in applying a source of heat causing thermal transfer of the direct dye(s) at the surface and/or inside the keratin materials. Preferably, the direct dye is applied to the keratin materials to be treated.

According to a first embodiment, the direct dye is applied to the keratin materials in the form of a divided solid, in free form. The expression free form is understood to mean that the direct dye does not exist in a form dispersed in a matrix.

According to one variant of this first embodiment, the direct dye is deposited in free form on a heat-resistant support. The keratin material, preferably hair, is applied to this support and the whole is heated by means of an instrument which releases heat. For example, a smoothing iron or a laser may be used.

According to a second embodiment of the invention, the direct dye is applied to the keratin materials in a divided solid form, in a non-free form. The direct dye is said to be in a non-free form when it is dispersed in a matrix. Advantageously, the direct dye is applied in the form of a film deposited or not deposited on a support.

In the case of this embodiment, the film comprises at least one film-forming polymer.

The period for which the heat source is applied is such that the keratin material is not substantially degraded. More particularly, the physical and physicochemical properties of the keratin material are not substantially impaired. There is furthermore no substantial modification of their natural colour, or modification of their mechanical resistance properties.

Thus, the higher the temperature, the shorter the duration of treatment.

By way of illustration, the duration is between 1 picosecond and 10 minutes.

The heat source may be provided in a conventional manner, such as for example a hair dryer, a hair dressing hood, a smoothing iron, a curling iron, a pulsed or non-pulsed laser system (a high-energy UV, visible or infrared light radiation), a heating tong system, and the like.

According to the method of the invention, a quantity of at least 0.0001 g of dye is deposited, by application, per gram of keratin material when it is in free form.

Furthermore, a quantity of at most 20 g of dye is deposited per gram of keratin material, more particularly at most 10 g of dye per gram of keratin material, and preferably at most 5 g of dye per gram of keratin material when it is in free form.

Advantageously, the keratin materials to which the film comprising the direct dye(s) is deposited are enclosed in a support which is resistant to heat under the application conditions. Furthermore, the support is aluminium foil, greaseproof paper or alternatively any synthetic material with a high glass transition temperature.

The operation may be carried out lock by lock or on the whole of the fibres.

Another subject of the present invention consists of a dry composition comprising at least one direct dye, and preferably at least one direct azo dye of formula (I) mentioned above, preferably in a state dispersed in the composition, and at least one film-forming polymer.

More particularly, the composition is provided in the form of a film deposited or not deposited on an appropriate support.

All the film-forming polymers are suitable for carrying out the invention, as long as they can be deposited by coating and remain cohesive once the film has been obtained and dried.

By way of examples of such film-forming polymers, reference may be made in particular to the manual International Cosmetic Ingredient Directory and Handbook 2000 edition, Volume 2, pages 1744 to 1747 which relates to film-forming compounds.

Among the polymers capable of entering into the composition of the films comprising the direct dye, there may be mentioned, for example, the polymers derived from vinylpyrrolidone, polyvinyl alcohol, polyurethanes, polymers derived from caprolactam, vinyllactam, vinyl acetate, polymers derived from acrylamide, polysaccharides capable of forming a film in the dry state such as cellulose derivatives, starches and derivatives, pullulan gum, gum arabic, pectins, alginates, carrageenans, galactomannans, agars, chitosans, chitins, polymers derived from hyaluronic acid, xanthan gum, karaya gum, proteins capable of forming a film in the dry state, such as gelatin, gluten, casein, zein, gliadin, hordein and their natural or synthetic derivatives, polymers derived from silicones, amphoteric or anionic polymers which are derived from monomers comprising at least one carboxylic, sulphonic or phosphoric functional group, acrylic copolymers of phosphorylcholine (lipidure), anion-cation complexes of the gum arabic/gelatin or gum arabic/chitosan type, or the collagen/GlycosAminoGlycan combination.

By way of suitable cationic film-forming polymers, there may be mentioned more particularly the following polymers, having in general a number-average molecular mass of between 500 and about 5 000 000:

-   (1) the homopolymers or copolymers derived from acrylic or     methacrylic esters or amides and comprising at least one of the     units of the following formulae:

in which:

-   R₁ and R₂, which are identical or different, each represent a     hydrogen atom or an alkyl group having from 1 to 6 carbon atoms; -   R₃ denotes a hydrogen atom or a CH₃ group; -   A is a linear or branched alkyl group of 1 to 6 carbon atoms, or a     hydroxyalkyl group of 1 to 4 carbon atoms; -   R₄, R₅, R₆, which are identical or different, represent an alkyl     group having from 1 to 18 carbon atoms or a benzyl group; -   X denotes a methosulphate anion or a halide such as chloride or     bromide; -   (2) the quaternized guar gums; -   (3) the quaternized copolymers of vinylpyrrolidone and     vinylimidazole; -   (4) the chitosans or their salts; -   the salts which can be used are in particular the acetate, lactate,     glutamate, gluconate or pyrrolidonecarboxylate of chitosan.

The copolymers of the family (1) contain, in addition, one or more units derived from comonomers which may be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen with lower (C₁₋₄) alkyls, groups derived from acrylic or methacrylic acids or esters thereof, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters.

Thus, among these copolymers of the family (1), there may be mentioned:

-   -   the copolymers of acrylamide and dimethylamino-ethyl         methacrylate quaternized with dimethyl sulphate or with a         dimethyl halide,     -   the copolymers of acrylamide and         methacryloyloxy-ethyltrimethylammonium chloride described, for         example, in Patent Application EP-A-080976,     -   the copolymers of acrylamide and         methacryloyloxy-ethyltrimethylammonium methosulphate,     -   the vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate         copolymers, quaternized or otherwise, such as the products sold         under the name “GAFQUAT®”, by the company ISP such as for         example “GAFQUAT® 734” or “GAFQUAT® 755” or alternatively the         products called “COPOLYMER® 845, 958 and 937”. These polymers         are described in detail in French Patents 2 077 143 and 2 393         573,     -   the dimethylaminoethyl         methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers such         as the product sold under the name GAFFIX® VC 713 by the company         ISP, and     -   the quaternized vinylpyrrolidone/dimethyl-aminopropyl         methacrylamide copolymer such as in particular the product sold         under the name “GAFQUAT® HS 100” by the company ISP.

Among these compounds, there may be mentioned chitosan having a degree of deacetylation of 90% by weight, pyrrolidone-chitosan carboxylate sold under the name KYTAMER® PC by the company AMERCHOL.

As regards the anionic film-forming polymers, the latter generally comprise at least one group derived from a carboxylic, sulphonic or phosphoric acid and have a number-average molecular mass of between about 500 and 5 000 000.

The carboxylic groups are more particularly provided by unsaturated mono- or dicarboxylic acid monomers such as those corresponding to the formula:

in which n is an integer from 0 to 10, A₁ denotes a methylene group, optionally linked to the carbon atom of the unsaturated group or to the neighbouring methylene group, when n is greater than 1, through a heteroatom such as oxygen or sulphur, Ra denotes a hydrogen atom, or a phenyl or benzyl group, Rb denotes a hydrogen atom, a C₁-C₄ alkyl group, in particular methyl, ethyl or carboxyl, Rc denotes a hydrogen atom or a lower alkyl group, a group —CH₂—COOH, or a phenyl or benzyl group.

The preferred anionic film-forming polymers with carboxylic groups are:

-   A) the homo- or copolymers of acrylic or methacrylic acid or their     salts and in particular the products sold under the names VERSICOL®     E or K by the company ALLIED COLLOID and ULTRAHOLD® by the company     BASF, the copolymers of acrylic acid and of acrylamide, the sodium     salts of the polyhydroxycarboxylic acids. -   B) The copolymers of acrylic or methacrylic acid with a monoethylene     monomer such as ethylene, styrene, vinyl esters, acrylic or     methacrylic acid esters, optionally grafted onto a polyalkylene     glycol such as polyethylene glycol and optionally crosslinked. Such     polymers are described in particular in French Patent 1 222 944 and     German Application 2 330 956, copolymers of this type containing in     their chain an acrylamide unit optionally N-alkylated and/or     hydroxyalkylated as described especially in Luxembourg Patent     Applications 75370 and 75371. There may also be mentioned the     copolymers of acrylic acid and C₁-C₄ alkyl methacrylate and the     terpolymers of vinylpyrrolidone, acrylic acid and C₁-C₂₀ alkyl, for     example lauryl, methacrylate such as that sold by the company ISP     under the name ACRYLIDONE® LM and the methacrylic acid/ethyl     acrylate/tert-butyl acrylate terpolymers such as the product sold     under the name LUVIMER® 100 P by the company BASF. -   C) The copolymers derived from crotonic acid such as those     containing in their chain vinyl propionate or acetate units and     optionally other monomers such as methallyl or allyl esters, vinyl     ether or vinyl ester of a linear or branched saturated carboxylic     acid with a long hydrocarbon chain such as those containing at least     5 carbon atoms, it being possible for these polymers to be     optionally grafted and crosslinked or alternatively another monomer     which is a vinyl, allyl or methallyl ester of an α- or β-cyclic     carboxylic acid. Such polymers are described, inter alia, in French     Patents 1 222 944, 1 580 545, 2 265 782, 2 265 781, 1 564 110 and 2     439 798. A commercial product entering into this class is the resin     28-29-30 sold by the company NATIONAL STARCH. -   D) The copolymers derived from C₄-C₈ monounsaturated carboxylic     acids or anhydrides chosen from:     -   the copolymers comprising (i) one or more itaconic, fumaric or         maleic acids or anhydrides and (ii) at least one monomer chosen         from vinyl esters, vinyl ethers, vinyl halides, phenylvinyl         derivatives, acrylic acid and its esters, the anhydride         functions of these copolymers being optionally monoesterified or         monoamidated. Such polymers are described in particular in         Patents U.S. Pat. Nos. 2,047,398, 2,723,248, 2,102,113 and         Patent GB 839805. Marketed products are especially those sold         under the names GANTREZ® AN or ES by the company ISP.     -   the copolymers comprising (i) one or more maleic, citraconic or         itaconic anhydride units and (ii) one or more monomers chosen         from allyl or methallyl esters optionally containing one or more         acrylamide, methacrylamide or α-olefin groups, acrylic or         methacrylic esters, acrylic or methacrylic acid or         vinylpyrrolidone in their chain, the anhydride functions of         these copolymers being optionally monoesterified or         monoamidated.

These polymers are, for example, described in French Patents 2 350 384 and 2 357 241 by the applicant.

-   E) The polyacrylamides containing carboxylate groups; -   F) the anionic polyurethanes, such as the product sold by BASF under     the name Luviset PUR.

The polymers comprising sulphonic groups are polymers containing vinylsulphonic, styrenesulphonic, naphthalenesulphonic or acrylamidoalkylsulphonic units.

These polymers may be especially chosen from:

-   -   the salts of polyvinylsulphonic acid having a molecular mass of         between about 1000 and 100 000 as well as the copolymers with an         unsaturated comonomer such as acrylic or methacrylic acids and         their esters as well as acrylamide or its derivatives, vinyl         ethers and vinylpyrrolidone.     -   the salts of polystyrenesulphonic acid such as the sodium salts         sold for example under the name Flexan® 130 by NATIONAL STARCH.         These compounds are described in Patent FR 2 198 719.     -   the salts of polyacrylamidesulphonic acids, such as those         mentioned in Patent U.S. Pat. No. 4,128,631 and more         particularly polyacrylamidoethylpropanesulphonic acid.

According to the invention, it is also possible to use film-forming anionic polymers of the grafted silicone type comprising a polysiloxane portion and a portion consisting of a nonsilicone organic chain, one of the two portions constituting the principal chain of the polymer, the other being grafted onto the said principal chain. These polymers are for example described in patent applications EP-A-/412 704, EP-A-/412 707, EP-A-/640 105 and WO 95/00578, EP-A-/582 152 and WO 93/23009 and patents U.S. Pat. Nos. 4,693,935, 4,728,571 and U.S. Pat. No. 4,972,037.

Such polymers are, for example, the copolymers which can be obtained by free-radical polymerization starting with a mixture of monomers, consisting of:

-   a) 50 to 90% by weight of tert-butyl acrylate; -   b) 0 to 40% by weight of acrylic acid; -   c) 5 to 40% by weight of silicone-containing macromer of formula:

with v being a number ranging from 5 to 700; the percentages by weight being calculated relative to the total weight of the monomers.

Further examples of grafted silicone polymers include in particular polydimethylsiloxanes (PDMS) onto which are grafted, via a chain link of thiopropylene type, mixed polymer units of poly(meth)acrylic acid type or of poly(alkyl (meth)acrylate) type, and polydimethylsiloxanes (PDMS) onto which are grafted, via a chain link of thiopropylene type, polymer units of poly(isobutyl(meth)acrylate) type.

It is also possible use, as film-forming polymers, functionalized polyurethanes, containing silicone or not.

The polyurethanes particularly sought by the present invention are those described in patents EP 0 751 162, EP 0 637 600, FR 2 743 297 and EP 0 648 485 and the patents EP 0 656 021 or WO 94/03510 and EP 0 619 111.

According to the invention, the anionic film-forming polymers are preferably chosen from the acrylic acid copolymers such as the acrylic acid/ethyl acrylate/N-tert-butylacrylamide terpolymers sold under the name ULTRAHOLD® STRONG by the company BASF, the copolymers derived from crotonic acid such as the vinyl acetate/vinyl tert-butylbenzoate/crotonic acid terpolymers and the crotonic acid/vinyl acetate/vinyl neododecanoate terpolymers sold in particular under the name Résine 28-29-30 by the company NATIONAL STARCH, the polymers derived from itaconic, fumaric and maleic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters such as the monoesterified maleic anhydride/methyl vinyl ether copolymers sold, for example, under the name GANTREZ® by the company ISP, the copolymers of methacrylic acid and of methyl methacrylate sold under the name EUDRAGIT® L by the company ROHM PHARMA, the copolymers of methacrylic acid and of ethyl acrylate sold under the name LUVIMER® MAEX or MAE by the company BASF and the vinyl acetate/crotonic acid copolymers and the vinyl acetate/crotonic acid copolymers grafted with polyethylene glycol sold under the name ARISTOFLEX® A by the company BASF and the polyurethane Luviset PUR® sold by the company BASF.

The anionic film-forming polymers which are most particularly preferred are those chosen from the monoesterified maleic anhydride/methyl vinyl ether copolymers sold under the name GANTREZ® ES 425 by the company ISP, the acrylic acid/ethyl acrylate/N-tert-butylacrylamide terpolymers sold under the name ULTRAHOLD® STRONG by the company BASF, the copolymers of methacrylic acid and of methyl methacrylate sold under the name EUDRAGIT® L by the company ROHM PHARMA, the vinyl acetate/vinyl tert-butylbenzoate/crotonic acid terpolymers and the crotonic acid/vinyl acetate/vinyl neododecanoate terpolymers sold under the name Résine 28-29-30 by the company NATIONAL STARCH, the copolymers of methacrylic acid and ethyl acrylate sold under the name LUVIMER® MAEX or MAE by the company BASF, the vinylpyrrolidone/acrylic acid/lauryl methacrylate terpolymers sold under the name ACRYLIDONE® LM by the company ISP and the polyurethane Luviset PUR® sold by the company BASF.

Among the amphoteric film-forming polymers which can be used, there may be mentioned those containing B and C units distributed randomly in the polymer chain where B denotes a unit which is derived from a monomer containing at least one basic nitrogen atom and C denotes a unit which is derived from an acidic monomer containing one or more carboxylic or sulphonic groups or alternatively B and C may denote groups which are derived from zwitterionic monomers of carboxybetaines or of sulphobetaines;

B and C may also denote a cationic polymer chain containing primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups carries a carboxylic or sulphonic group linked via a hydrocarbon group or alternatively B and C form part of a chain of a polymer with an α-dicarboxylic ethylene unit in which one of the carboxylic groups has been caused to react with a polyamine containing one or more primary or secondary amine groups.

The amphoteric film-forming polymers corresponding to the definition given above which are more particularly preferred are chosen from the following polymers:

-   (1) The polymers resulting from the copolymerization of a monomer     derived from a vinyl compound carrying a carboxylic group such as     more particularly acrylic acid, methacrylic acid, maleic acid,     alpha-chloroacrylic acid, and of a basic monomer derived from a     substituted vinyl compound containing at least one basic atom     (preferably an amino functional group) such as more particularly     dialkylaminoalkyl methacrylate and acrylate,     dialkylaminoalkylmethacrylamide and -acrylamide. Such compounds are     described in American U.S. Pat. No. 3,836,537. There may also be     mentioned the sodium acrylate/acrylamidopropyltrimethylammonium     chloride copolymer sold under the name POLYQUART KE 3033 by the     company HENKEL.

The vinyl compound may also be a dialkyldiallylammonium salt such as diethyldiallylammonium chloride. The copolymers of acrylic acid and the latter monomer are offered under the names MERQUAT 280, MERQUAT 295 and MERQUAT PLUS 3330 by the company CALGON.

-   (2) The polymers containing units which are derived from:     -   a) at least one monomer chosen from acrylamides or         methacrylamides substituted on the nitrogen atom by an alkyl         group,     -   b) at least one acidic comonomer containing one or more reactive         carboxylic groups, and     -   c) at least one basic comonomer such as esters with primary,         secondary, tertiary and quaternary amine substituents of acrylic         and methacrylic acids and the product of quaternization of         dimethylaminoethyl methacrylate with dimethyl or diethyl         sulphate.

The N-substituted acrylamides or methacrylamides more particularly preferred are compounds whose alkyl groups contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide as well as the corresponding methacrylamides.

The acidic comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic and fumaric acids as well as the alkyl monoesters having 1 to 4 carbon atoms of maleic or fumaric anhydrides or acids.

The basic comonomers preferred are methacrylates of aminoethyl, butylaminoethyl, N,N′-dimethylaminoethyl, N-tert-butylaminoethyl.

Particularly used are the copolymers whose CTFA name (4th ed., 1991) is Octylacrylamide/acrylates/butyl-aminoethyl methacrylate copolymer such as the products sold under the name AMPHOMER® or LOVOCRYL® 47 by the company NATIONAL STARCH.

-   (3) The partially or completely acylated and crosslinked     polyaminoamides derived from polyaminoamides of general formula:

in which R₁₀ represents a divalent group derived from a saturated dicarboxylic acid, a mono- or dicarboxylic aliphatic acid with ethylenic double bond, an ester of a lower alkanol having 1 to 6 carbon atoms of these acids or a group which is derived from the addition of any one of the said acids with a bis-primary or bis-secondary amine, and Z denotes a group which is derived from a bis-primary, mono- or bis-secondary polyalkylene-polyamine and preferably represents:

-   a) in the proportions of 60 to 100 mol %, the group

where x=2 and p=2 or 3, or alternatively x=3 and p=2 this group being derived from diethylenetriamine, triethylenetetraamine or dipropylenetriamine;

-   b) in the proportions of 0 to 40 mol %, the group (IV) above, in     which x=2 and p=1 and which is derived from ethylenediamine, or the     group which is derived from piperazine:

-   c) in the proportions of 0 to 20 mol %, the group —NH—(CH₂)₆—NH—     which is derived from hexamethylenediamine, these polyamino amides     being crosslinked by adding a bifunctional crosslinking agent chosen     from the epihalohydrins, diepoxides, dianhydrides, bis-unsaturated     derivatives, by means of 0.025 to 0.35 mol of crosslinking agent per     amine group of the polyamino amide and acylated by the action of     acrylic acid, chloroacetic acid or of an alkanesultone or of their     salts.

The saturated carboxylic acids are preferably chosen from the acids having 6 to 10 carbon atoms such as adipic, 2,2,4-trimethyladipic and 2,4,4-trimethyladipic acids, terephthalic acid, the acids with ethylene double bond such as for example acrylic, methacrylic and itaconic acids.

The alkanesultones used in the acylation are preferably propane- or butanesultone, the salts of the acylating agents are preferably the sodium or potassium salts.

-   (4) The polymers containing zwitterionic units of formula:

in which R₁₁ denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer from 1 to 3, R₁₂ and R₁₃ represent a hydrogen atom or a methyl, ethyl or propyl group, R₁₄ and R₁₅ represent a hydrogen atom or an alkyl group such that the sum of the carbon atoms in R₁₄ and R₁₅ does not exceed 10.

The polymers comprising such units may also comprise units derived from nonzwitterionic monomers such as dimethyl- or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides or vinyl acetate.

By way of example, there may be mentioned the copolymers of methyl methacrylate/N,N-dimethylcarboxyaminoethyl methacrylate.

-   (5) The polymers derived from chitosan containing monomeric units     corresponding to the following formulae:

the (D) unit being present in proportions of between 0 and 30%, the (E) unit in proportions of between 5 and 50% and the (F) unit in proportions of between 30 and 90%, it being understood that in this (F) unit, R₁₆ represents a group of formula:

in which if q=0, R₁₇, R₁₈ and R₁₉, which are identical or different, each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamine residue or a dialkylamine residue optionally interrupted by one or more nitrogen atoms and/or optionally substituted with one or more amine, hydroxyl, carboxyl, alkylthio or sulphonic groups, or an alkylthio residue whose alkyl group carries an amino residue, at least one of the R₁₇, R₁₈ and R₁₉ groups being in this case a hydrogen atom; or if q=1, R₁₇, R₁₈ and R₁₉ each represent a hydrogen atom, as well as the salts formed by these compounds with bases or acids.

-   (6) The polymers corresponding to the general formula (VI) are     described for example in French Patent 1 400 366 and comprising the     repeating unit below:

in which R₂₀ represents a hydrogen atom, a CH₃O, CH₃CH₂O or phenyl group, R₂₁ denotes a hydrogen atom or a lower alkyl group such as methyl or ethyl, R₂₂ denotes a hydrogen atom or a C₁-C₆ lower alkyl group such as methyl or ethyl, R₂₃ denotes a C₁-C₆ lower alkyl group such as methyl or ethyl or a group corresponding to the formula: —R₂₄—N(R₂₂)₂, R₂₄ representing a group —CH₂—CH₂—, —CH₂—CH₂—CH₂— or —CH₂—CH(CH₃)—, R₂₂ having the meanings mentioned above.

-   (7) The polymers derived from the N-carboxyalkylation of chitosan     such as N-carboxymethyl chitosan or N-carboxybutyl chitosan. -   (8) The amphoteric polymers of the -D-X-D-X— type chosen from: -   a) the polymers obtained by the action of chloroacetic acid or     sodium chloroacetate on the compounds containing at least one unit     of formula:     -D-X-D-X-D-  (VII)     where D denotes a group

and X denotes the symbol E or E′, E and E′, which are identical or different, denote a bivalent group which is an alkylene group with a linear or branched chain containing up to 7 carbon atoms in the principal chain which is unsubstituted or substituted with hydroxyl groups and which may contain, in addition, oxygen, nitrogen or sulphur atoms, 1 to 3 aromatic and/or heterocyclic rings; the oxygen, nitrogen and sulphur atoms being present in the form of ether, thioether, sulphoxide, sulphone, sulphonium, alkylamine or alkenylamine groups, or hydroxyl, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and/or urethane groups.

-   b) The polymers of formula:     -D-X-D-X-  (VII′)     where D denotes a group

and X denotes the symbol E or E′ and, at least once, E′; E having the meaning indicated above and E′ is a bivalent group which is an alkylene group with a linear or branched chain having up to 7 carbon atoms in the principal chain, which is unsubstituted or substituted with one or more hydroxyl groups and containing one or more nitrogen atoms, the nitrogen atom being substituted with an alkyl chain optionally interrupted by an oxygen atom and necessarily containing one or more carboxyl functional groups or one or more hydroxyl functional groups and betainized by reaction with chloroacetic acid or sodium chloroacetate.

-   (9) The (C₁-C₅)alkyl vinyl ether/maleic anhydride copolymers     partially modified by semiamidation with an     N,N-dialkylaminoalkylamine such as N,N-dimethylamino-propylamine or     by semiesterification with an N,N-dialkylaminoalkanol. These     copolymers may also contain other vinyl comonomers such as     vinylcaprolactam.

The preferred amphoteric film-forming polymers are those of the family (3) such as the copolymers whose CTFA name is Octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer such as the products sold under the names AMPHOMER®, AMPHOMER® LV 71 or LOVOCRYL® 47 by the company NATIONAL STARCH and those of the family (4) such as the butyl methacrylate/N,N-dimethylcarboxyaminoethyl methacrylate copolymers.

The nonionic film-forming polymers which can be used according to the present invention are chosen for example from:

-   -   the homopolymers of vinyl acetate;     -   the copolymers of vinyl acetate and acrylic ester;     -   the copolymers of vinyl acetate and ethylene;     -   the copolymers of vinyl acetate and maleic ester, for example         dibutyl maleate;     -   the copolymers of acrylic esters such as for example the         copolymers of alkyl acrylates and alkyl methacrylates such as         the products offered by the company ROHM & HAAS under the names         PRIMAL® AC-261 K and EUDRAGIT® NE 30 D, by the company BASF         under the name 8845, by the company HOECHST under the name         APPRETAN® N9212;     -   the copolymers of acrylonitrile and of a nonionic monomer chosen         for example from butadiene and alkyl (meth)acrylates; there may         be mentioned the products offered under the name CJ 0601 B by         the company ROHM & HAAS;     -   the homopolymers of styrene;     -   the copolymers of styrene and alkyl (meth)acrylate such as the         products MOWILITH® LDM 6911, MOWILITH® DM 611 and MOWILITH®LDM         6070 offered by the company HOECHST, the products RHODOPAS® SD         215 and RHODOPAS® DS 910 offered by the company RHODIA CHIMIE;     -   the copolymers of styrene, alkyl methacrylate and alkyl         acrylate;     -   the nonionic polyurethanes;     -   the copolymers of styrene and butadiene;     -   the copolymers of styrene, butadiene and vinylpyridine;     -   the copolymers of alkyl acrylate and urethane;     -   the polyamides;     -   the homopolymers and copolymers of vinyllactam.

The alkyl groups of the nonionic polymers mentioned above preferably have from 1 to 6 carbon atoms.

According to the present invention, the film-forming polymers are preferably nonionic polymers, and better still nonionic polymers with vinyllactam units. They are described in particular in Patents U.S. Pat. Nos. 3,770,683, 3,929,735, 4,521,504, 5,158,762, 5,506,315 and in Patent Applications WO 94/121148, WO 96/06592 and WO 96/10593. They may be provided in pulverulent form or in the form of a solution or a suspension.

The homopolymers or copolymers with vinyllactam units comprise units of formula (IX):

in which n is independently 3, 4 or 5.

The number-average molecular mass of the polymers with vinyllactam units is generally greater than about 5000, preferably between 10 000 and 1 000 000 approximately, more preferably between 10 000 and 100 000 approximately.

It is possible to use, in particular, as film-forming polymer, in the present invention, polyvinyl-pyrrolidones such as those marketed under the name Luviskol® K30 by the company BASF; polyvinylcaprolactams such as those marketed under the name Luviskol® PLUS by the company BASF; poly(vinylpyrrolidone/vinyl acetate) copolymers such as those marketed under the name PVPVA® S630L by the company ISP, Luviskol® VA 73, VA 64, VA 55, VA 37 and VA 28 by the company BASF; and poly(vinylpyrrolidone/vinyl acetate/vinyl propionate) terpolymers such as for example those marketed under the name Luviskol® VAP 343 by the company BASF.

According to this second embodiment, the composition, in film form, may comprise at least one plasticizer.

The plasticizers conventionally used in the field may be used in the composition.

However, by way of more specific examples, there may be mentioned, inter alia, urea, glycerine, sorbitol, mono- and/or disaccharides, dipropylene glycol, butylene glycol, pentylene glycol or polyethylene glycol, benzyl alcohol, or mixtures thereof.

Advantageously, the film may contain at least one formulation adjuvant and/or cosmetic active agent chosen for example from dispersing agents such as alkali metal lignosulphonates, antioxidants, pH-regulating agents, perfumes, silicones, ceramides.

Usually, the content of adjuvant in the composition represents, for each, from 0.01 to 20% each; the total content of additives, if they are present, not exceeding 80% by weight of the dry solid composition.

The composition according to the invention may additionally be in the form of a film deposited or not deposited on a support.

If the support is present, the latter is advantageously chosen from compounds which are not degraded under the conditions for carrying out the method.

The support is chosen from compounds which do not become solubilized under the conditions for preparing the said film. Thus, the support is not soluble in an aqueous medium.

Furthermore, the support may be chosen from compounds which conduct electricity or from compounds which are electrical insulators.

The water-soluble or water-insoluble support may thus be made of a material chosen from polyurethanes, thermoplastic elastomers of the type including styrene-butadiene-styrene, styrene-ethylene-butadiene-styrene, ethylene-vinyl acetate, or coether ester, poly-ethylenes, polypropylenes, or silicones.

Such supports are sold in particular under the trade marks: BAYDUR®, DALTOFLEX®, UROFLEX®, HYPERLAST®, INSPIRE®, DESMOPAN®, ESTANE®, LASTANE®, TEXIN®, CARIFLEX®, KRATON®, SOLPRENE®, ELVAX®, ESCORENE®, OPTENE®, ARNITEL®, HYTREL®, or RITEFLEX®.

It would not be excluded to choose, as support, an inorganic compound such as for example aluminium.

It is specified that the thickness of the support on which the composition is deposited preferably has a thickness which allows easy use for dyeing the keratin materials (easy folding, sufficient solidity to allow several applications with several foldings and unfoldings).

Usually, the thickness of the support is preferably between 0.01 mm and 2 mm, and preferably between 0.02 and 0.2 mm.

Furthermore, when the composition is deposited on a support, the thickness of the film made of the composition is usually between 20 μm and 1000 μm, and preferably between 50 μm and 200 μm.

In the case where the composition is in the form of a film not deposited on a support, the thickness of the film made of the composition is close to 0.01 mm to 2 mm, preferably 0.02 to 0.2 mm.

Another subject of the invention consists of a method for preparing a composition in the form of a film.

More particularly, a method consists in carrying out the following steps:

-   a) a composition comprising at least one dye of formula (I), at     least one film-forming polymer and at least one solvent is prepared; -   b) a film made of the composition thus obtained is deposited on an     appropriate support; -   c) the solvent is evaporated.

The solvent entering into the composition is chosen from the compounds which solubilize or disperse at least the film-forming polymer. In the latter case, the film-forming polymers are in the form of dispersions of solid or liquid particles of polymer (latex or pseudolatex).

Moreover, the solvent furthermore has a boiling point less than the sublimation temperature of the dye and less than the degradation temperature of the film-forming polymer. Advantageously, the boiling point of the solvent is less than or equal to 110° C.

By way of examples of solvents which can be used, there may be mentioned for example water, ethanol, acetone, isopropanol, ethyl acetate, dichloromethane, ethyl ether and the like.

Preferably, the composition comprises from 5 to 99.9% by weight of solvent.

It should be noted, advantageously, that the composition comprises from 0.0001 to 60% of direct dye.

Moreover, according to a particular embodiment, the composition comprises from 0.01 to 80% by weight of film-forming polymer.

Once the composition has been obtained, it is deposited on an appropriate support, such as for example a non-rough and horizontal support of the heating or non-heating bed or marble type.

It should be specified that, advantageously, the composition is deposited directly on the support with which the composition is intended to be used for dyeing, if such a variant is chosen.

It is preferable for the thickness of the composition deposited to be relatively uniform.

Furthermore, the thickness of the composition deposited is such that a film is obtained, preferably after evaporation of the solvent, which can be handled at room temperature (more particularly between 15 and 30° C.). Without limitation, the thickness of the composition deposited varies in general from 0.01 to 2 mm, preferably from 0.02 to 2 mm.

The composition is deposited in a conventional manner, without, but preferably with, an apparatus which makes it possible to obtain a substantially uniform film thickness.

After depositing the composition, the solvent is evaporated in a conventional manner.

The film obtained is then separated from its support and then deposited on the materials to be treated.

Concrete but nonlimiting examples of the invention will now be presented.

EXAMPLES

1. Preparation of a Dyed Film

The following mixture is prepared, with stirring for 20 minutes

Constituent Concentration Dye 2% Hydroxypropylcellulose sold under the 1.5% name Klucel MF by the company Aqualon Ethanol qs. 100% and deposited on a heating plate at 60° C. The dyed film is formed by evaporation of the ethanol.

2. Hair Dyeing

The film obtained above is applied to natural hair which is 90% white.

Each lock is then covered with aluminium foil.

Heat is applied by means of a Japanese smoothing iron

Thermal Effect Iron (temperature and duration indicated in the table below).

At the end of the treatment, the locks are dyed.

No rinsing is necessary.

The colour of each lock is then measured (Minolta CM3600d spectrocolorimeter, specular components included, angle 10°, illuminant D65).

3. Colorimetric Results

T T° C. (min) L* Control — — 61.3 Dye 1 180 5 39.5 Dye 2 180 5 36.8 Dye 3 180 5 31.3 Dye 7 180 5 42.3 Dye 4 180 5 25.4 Dye 5 180 5 31.3 Dye 6 185 1 39.0 

1. A method for dyeing human keratin materials, comprising: applying at least one direct azo dye contained in a dry composition directly to or close to the keratin materials, and applying heat; wherein the at least one direct azo dye is chosen from azo dyes of formula (I):

wherein: n and n′ are integers that are independently chosen from 1 to 5; R and R′ are independently chosen from: a hydrogen atom; a saturated, unsaturated, aromatic, linear, branched, or cyclic, C₁-C₃₀ hydrocarbon chain that is optionally substituted with at least one group chosen from halogen atoms, hydroxyl, nitro, cyano, carboxylic acid, allyl, haloallyl, C₁-C₁₀ alkoxy, (C₁-C₄)alkylcarbonyl(C₁-C₄)amino, (C₁-C₄)alkylaminocarbonyl, hydrogeno -carbonylamino, (C₁-C₄)alkylsulphonylamino, (C₁-C₄)alkoxycarbonylamino, (C₁-C₄)alkoxycarbonyl, (C₁-C₄)alkylcarbonyl(C₁-C₄)alkoxycarbonyl, CF₃, and amino optionally substituted with at least one radical chosen from C₁-C₁₀ alkyl, C₁-C₁₀ hydroxyalkyl, alkoxy(C₁-C₁₀)alkyl, C₁-C₁₀ aminoalkyl, (C₁-C₁₀)(di)alkyl -amino(C₁-C₁₀)alkyl, C₁-C₁₀ cyanoalkyl, C₆-C₃₀ aryl, (C₆-C₃₀)aryl(C₁-C₄)alkyl, (C₄-C₃₀)cyclo(C₁-C₁₂)alkyl, (C₁-C₄)alkylcarbonyl, (C₁-C₄)alkylcarboxy(C₁-C₄)alkyl, allyl, and haloallyl radicals; and optionally interrupted or attached to the aromatic ring to which they are attached by at least one heteroatom or group comprising at least one heteroatom, wherein said at least one heteroatom is chosen from O, S, and N; and a hydroxyl group, C₁-C₄ alkoxy, carboxylic acid, halogen, allyl, hydrogenocarbonyl, trifluoromethyl, nitro, cyano, and amino optionally substituted with at least one radical chosen from C₁-C₄ alkyl, C₂-C₄ alkenyl, C₁-C₄ cyanoalkyl, C₁-C₄ hydroxyalkyl, C₆-C₃₀ aryl, (C₆-C₃₀)aryl(C₁-C₄)alkyl, allyl, (C₁-C₄)alkoxy(C₁-C₄)alkyl, (C₄-C₃₀)cyclo(C₁-C₁₂)alkyl, (C₁-C₄)alkylcarbonyl, (C₁-C₄)alkylcarboxy(C₁-C₄)alkyl, haloallyl, C₁-C₄ amino-alkyl, (C₁-C₄)(di)alkylamino(C₁-C₄)alkyl, (C₁-C₄)alkylsulphonyl, and (C₁-C₄)alkoxycarbonyl radicals; wherein: at least one of radicals R or R′ is chosen from hydroxyl, nitro, cyano, and amino optionally substituted with at least one radical; and two radicals of R or R′ attached to two adjacent carbon atoms may optionally form, together with the aromatic ring carrying the carbon atoms to which each is attached, a fused napthalene ring that is optionally substituted with at least one group chosen from aminosulphonyl and (C₁-C₄)alkyl(C₁-C₄)aminosulphonyl.
 2. The method according to claim 1, wherein the at least one direct azo dye is chosen from azo dyes of formula (Ia):

wherein: R′₁ is chosen from a hydrogen atom, an amino group, and a hydroxyl group; R′₂ is chosen from a hydrogen atom, a halogen atom, a carboxylic acid group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, an allyl group, and a C₁-C₄ aminocarbonylalkyl group; R′₃ is chosen from a hydrogen atom, a hydroxyl group, and NR″₁R″₂, wherein R″₁ and R″₂ are independently chosen from a hydrogen atom, a C₁-C₄ alkyl group, a C₂-C₄ alkenyl group, a C₁-C₄ cyanoalkyl group, a C₁-C₄ hydroxyalkyl group, a C₆-C₃₀ aryl group, a (C₆-C₃₀)aryl(C₁-C₄)alkyl group, an allyl group, a (C₁-C₄) -alkoxy(C₁-C₄)alkyl group, a (C₄-C₃₀)cyclo(C₁-C₁₂)alkyl group, a (C₁-C₄)alkyl -carbonyl group, a (C₁-C₄)alkylcarboxy(C₁-C₄)alkyl group or a haloallyl group, a C₁-C₄ aminoalkyl group, and a (C₁-C₄)(di)alkylamino(C₁-C₄)alkyl group; R′₂ and R′₃ may optionally form, together with the benzene ring to which they are attached, a fused naphthalene ring that is optionally substituted with at least one —SO₂—NHR group, wherein R is chosen from a hydrogen atom and an optionally substituted C₁-C₄ alkyl chain; R′₄ is chosen from a hydrogen atom, a halogen atom, a hydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, and a (C₁-C₄)alkoxy(C₁-C₄)alkyl group; R′₅ is chosen from a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a (C₁-C₄)alkylcarbonylamino group, a formylamino group, a (C₁-C₄)alkylsulphonylamino group, a (C₁-C₄)alkoxycarbonylamino group, and a CF₃ group; R′₄ and R′₅ may optionally form, together with the benzene ring to which they are attached, a fused naphthalene ring; R₅ is chosen from a hydrogen atom, a halogen atom, a carboxylic acid group, a hydroxyl group, an amino group, a cyano group and a C₁-C₄ alkyl group; R₄ is chosen from a hydrogen atom and a nitro group; R₃ is chosen from a hydrogen atom, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a (C₄-C₃₀)cyclo(C₁-C₁₂)alkyl group, a C₂-C₄ alkenyl group, a C₁-C₄ alkoxycarbonyl group, a (C₁-C₄)alkylcarbonyl group, a (C₁-C₄)alkoxycarbonyl(C₁-C₄)alkoxycarbonyl group, a (C₁-C₄)alkylcarbonyl(C₁-C₄)alkoxycarbonyl group, an aryl group, an amino group, a nitro group, a cyano group, and a CF₃ group; R₂ is chosen from a hydrogen atom, a nitro group, and a C₁-C₄ alkyl group; R₁ is chosen from a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, and a cyano group; and wherein at least one of radicals R′₁ to R′₅ and R₁ to R₅ is chosen from hydroxyl, nitro, cyano, and amino optionally substituted with at least one radical.
 3. The method according to claim 2, wherein R₁, R₂, R′₁, R′₂, and R₄ are hydrogen atoms.
 4. The method according to claim 2, wherein R′₃ is chosen from a hydrogen atom and an NR″₁R″₂ group, wherein R″₁ and R″₂ are independently chosen from a hydrogen atom, a C₁-C₄ alkyl group, a C₁-C₄ cyanoalkyl group, a C₁-C₄ hydroxyalkyl group, and a C₁-C₄ aminoalkyl group.
 5. The method according to claim 2, wherein R′₄ is a hydrogen atom; R′5 is chosen from a hydrogen atom and a C₁-C₄ alkyl group; and R′₄ and R′₅ may optionally form a fused naphthalene ring.
 6. The method according to claim 2, wherein R₃ is chosen from an amino group or a nitro group.
 7. The method according to claim 2, wherein R₅ is chosen from a hydrogen atom, a halogen atom, and an amino group.
 8. The method according to claim 1, wherein the at least one direct azo dye is chosen from compounds having an enthalpy of evaporation less than or equal to 200 kJ/mol.
 9. The method according to claim 1, wherein the at least one direct azo dye is chosen from Solvent Brown 1, Solvent Orange 1, Solvent Orange 7, Solvent Yellow 2, Solvent Yellow 3, Solvent Yellow 7, Solvent Yellow 14, Disperse Orange 1, Disperse Orange 3, Disperse Orange 25, Disperse Red 1, Disperse Red 13, Disperse Red 19, Disperse Red 50, Disperse Yellow 3, Mordant Brown 4, Mordant Brown 6, Mordant Brown 24, Mordant Brown 48, Mordant Orange 1, Pigment Red 3, 4-dimethylamino-2-methylazobenzene, 2-(4-diethylaminophenylazo)benzoic acid, N-ethyl-N-(2-aminoethyl)-4-(4-nitrophenylazo)aniline, N,N-hydroxyethyl-4-(4-nitrophenylazo)-2-methylaniline, N,N-hydroxyethyl-4-(4-aminophenylazo)-2aniline, and mixtures thereof.
 10. The method according to claim 1, wherein the source of heat is at a temperature in a range from 100° C. to 500° C.
 11. The method according to claim 10, wherein the duration of heating is such that the human keratin material is not substantially degraded.
 12. The method according to claim 11, wherein the duration of heating ranges from 1 picosecond to 10 minutes.
 13. The method according to claim 1, wherein the at least one direct azo dye is present in an amount of at least 0.0001 g per gram of keratin material in free form.
 14. The method according to claim 13, wherein the at least one direct azo dye is present in an amount of at most 20 g of dye per gram of human keratin material in free form.
 15. The method according to claim 1, comprising applying the at least one direct azo dye to the human keratin materials in the form of a divided solid, either in a free, or non-free form.
 16. The method according to claim 1, comprising applying the at least one direct azo dye to the human keratin materials in the form of a film.
 17. The method according to claim 16, wherein the film comprises at least one film-forming polymer.
 18. The method according to claim 16, wherein the film comprises at least one plasticizer.
 19. The method according to claim 17, wherein the film further comprises at least one plasticizer.
 20. The method according to claim 16, comprising depositing the film on a support which is not degraded under the conditions for carrying out the method. 